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The silicides Sc T  2 Si 2  ( T  = Ru, Rh, Os) were synthesized by arc-melting of the elements and subsequent annealing in sealed silica ampoules. They crystallize with the rarely observed HfFe 2 Si 2  type structure, space group  Pbcm . The structures of ScRu 2 Si 2  ( a  = 761.64(4),  b  = 730.70(6),  c  = 521.07(6) pm, w R  = 0.0314, 633  F  2  values, 31 variables) and ScOs 2 Si 2  ( a  = 771.10(8),  b  = 736.68(7),  c  = 521.88(5) pm, w R  = 0.0479, 623  F  2  values, 31 variables) were refined from single crystal X-ray diffractometer data. The refinements showed small degrees of Ru/Si respectively Os/Si mixing on one 4 c  site, leading to the refined compositions ScRu 1.96(1) Si 2.04(1)  and ScOs 1.91(1) Si 2.09(1) . The monomeric building units in both structures are two slightly distorted, crystallographically independent RuSi 5  respectively OsSi 5  square pyramids, which are condensed via common edges. The resulting densely packed [Ru 2 Si 2 ] and [Os 2 Si 2 ] networks leave voids for the scandium atoms with coordination number 18: Sc@Si 8 Ru 8 Sc 2  and Sc@Si 8 Os 8 Sc 2 . Temperature dependent magnetic susceptibility measurements of ScRu 2 Si 2  and ScOs 2 Si 2  indicate Pauli paramagnetism. Solid-state  29 Si and  45 Sc static and MAS NMR spectroscopy reveal significant Knight shifts and a strong influence of the  T /Si mixing on the experimental NMR line shapes. A larger overall  29 Si magnetic shift for ScRu 2 Si 2  compared to ScOs 2 Si 2 , although with a negative sign for one of the  29 Si resonances, suggests stronger paramagnetic effects for ScRu 2 Si 2 , in agreement with the magnetic susceptibility measurements.

The HfFe 2 Si 2 type silicides Sc T 2 Si 2 ( T = Ru, Rh, Os) – structure and solid-state 29 Si/ 45 Sc NMR spectroscopy